Examination of cobalt "picket fence" porphyrin and its complex with 1-methylimidazole as catalysts for the electroreduction of dioxygen

被引:42
作者
Steiger, B [1 ]
Anson, FC [1 ]
机构
[1] CALTECH, Arthur Amos Noyes Lab Chem Phys, Div Chem & Chem Engn, Pasadena, CA 91125 USA
关键词
D O I
10.1021/ic000537d
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The electrochemical behavior of cobalt 5,10,15,20-tetrakis(alpha,alpha,alpha,alpha-2-pivalamidophenyl)porphyrin (Co(II)TpivPP) was examined in benzonitrile solutions. The electrochemical responses were changed significantly by the addition of 1-methylimidazole which coordinates once to the Co(II) and twice to the Co(III) porphyrin. The corresponding equilibrium binding constants were estimated as 2.9 x 10(3) M-1 and 1.7 x 10(20);M-2. The cyclic voltammetric responses were affected by the rates of the ligand association/dissociation reactions, Formation of the O-2 adduct of the Co(II) porphyrin resulted in only small changes in the cyclic voltammetric pattern. Comparison between Co(II)TpivPP and cobalt :tetraphenylporphyrin ((CoTPP)-T-II) as catalysts for the electroreduction of O-2 showed the latter to be the superior catalyst both when adsorbed on graphite electrodes and when dissolved in thin layers of acidified benzonitrile where Co(II)TpivPP exhibited unimpressive catalytic activity compared with (CoTPP)-T-II, which appeared to catalyze the reduction of O-2 by significantly more than 2 electrons per molecule.
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页码:4579 / 4585
页数:7
相关论文
共 18 条
[1]   ON PREPARATION OF METALLOPORPHYRINS [J].
ADLER, AD ;
LONGO, FR ;
KAMPAS, F ;
KIM, J .
JOURNAL OF INORGANIC & NUCLEAR CHEMISTRY, 1970, 32 (07) :2443-&
[2]   A SIMPLIFIED SYNTHESIS FOR MESO-TETRAPHENYLPORPHIN [J].
ADLER, AD ;
LONGO, FR ;
FINARELLI, JD ;
GOLDMACH.J ;
ASSOUR, J ;
KORSAKOF.L .
JOURNAL OF ORGANIC CHEMISTRY, 1967, 32 (02) :476-+
[3]  
BARNETT GH, 1973, TETRAHEDRON LETT, P2887
[4]  
DRAGO RS, 1977, PHYSICAL METHODS CHE, P88
[5]   REVERSIBLE 2-ELECTRON ONE-PROTON SYSTEMS IN THE RING-CENTERED OXIDATION OF METALLOPORPHYRINS BEARING SECONDARY AMIDE-LINKED SUPERSTRUCTURES [J].
ELKASMI, A ;
LEXA, D ;
MAILLARD, P ;
MOMENTEAU, M ;
SAVEANT, JM .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (05) :1586-1595
[6]   THE ELECTROCHEMISTRY OF METALLOPORPHYRINS IN NONAQUEOUS MEDIA [J].
KADISH, KM .
PROGRESS IN INORGANIC CHEMISTRY, 1986, 34 :435-605
[7]  
Levich V. G., 1962, PHYSICOCHEMICAL HYDR
[8]   THE ELECTROCHEMISTRY OF VITAMIN-B12 [J].
LEXA, D ;
SAVEANT, JM .
ACCOUNTS OF CHEMICAL RESEARCH, 1983, 16 (07) :235-243
[9]   RELATION BETWEEN THE REDUCTION POTENTIALS OF ADSORBED AND UNADSORBED COBALT(III) TETRAKIS(N-METHYLPYRIDINIUM-4-YL)PORPHYRIN AND THOSE WHERE IT CATALYZES THE ELECTROREDUCTION OF DIOXYGEN [J].
NI, CL ;
ANSON, FC .
INORGANIC CHEMISTRY, 1985, 24 (26) :4754-4756
[10]   MOLECULAR ADDITION COMPOUNDS OF IODINE .1. AN ABSOLUTE METHOD FOR THE SPECTROSCOPIC DETERMINATION OF EQUILIBRIUM CONSTANTS [J].
ROSE, NJ ;
DRAGO, RS .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1959, 81 (23) :6138-6141